CN1204149C - Improved olefin polymerization process - Google Patents

Improved olefin polymerization process Download PDF

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CN1204149C
CN1204149C CNB99802631XA CN99802631A CN1204149C CN 1204149 C CN1204149 C CN 1204149C CN B99802631X A CNB99802631X A CN B99802631XA CN 99802631 A CN99802631 A CN 99802631A CN 1204149 C CN1204149 C CN 1204149C
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alkyl
silane
amino
monomer
polymerization
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CN1289343A (en
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R·E·小卡姆普贝尔
D·D·戴沃里
K·P·佩尔
F·J·提莫斯
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Dow Global Technologies LLC
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    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
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Abstract

A process for preparing homopolymers and copolymers of addition polymerizable monomers, or mixtures of such monomers, and the resulting polymer, wherein the process comprising contacting said monomer or mixture under high monomer conversion polymerization conditions with a catalyst composition comprising: a) a catalyst system comprising a Group 3-10 metal complex; and c) a silane, or hydrocarbylsilane corresponding to the formula: JjSiH4-j or AnJjSiH4-(n+j) wherein: J is C1-40 hydrocarbyl, A is a C2-20 alkenyl group, n is 1 or 2, and j is 0 or 1; wherein the polymer comprises from 0.1 to 100 long chain branches per 10,000 carbons, and at least some of which comprise a silane branching center.

Description

Improved olefine polymerizing process
Technical field
But the present invention relates to method, but described addition polymerization monomer is for example ethene or propylene or one or more olefinic monomer such as ethene and one or more C with the polymkeric substance of the catalyst composition polymerization addition polymerization monomer production height long chain branching (LCB) that comprises 3-10 family metal complexes and silane or hydrocarbyl si lanes branching agent 3-8But the alpha-olefin and the optional mixture of one or more copolymerization diolefine.Resulting polymers is applicable to by methods such as molding or curtain coatings and prepares solid article and goods such as moulded product, film, sheet material and foam article.
Background technology
WO97/42234 discloses a kind of method of polymkeric substance of the vinylidene aromatic monomer that utilizes the stereospecific structure that group-4 metal coordination catalyst and hydrocarbyl si lanes or dialkyl silane auxiliary agent prepare high degree of syndiotacticity.JACS, 1995,117, described among the 10747-19748 with silane metallocenes as the olefinic polymerization of catalyzer in as chain-transfer agent.The product that forms comprises the end capped polyolefine of silyl.
Disclose some LCB among the US-A-5 272 236,5 278 272,5 525 695 and be the Alathon of at least 3 chain/10000 carbon and ethylene/alpha-olefin copolymer and preparation method thereof, the oligopolymer or the polymkeric substance that wherein disclose the ethenyl blocking that produces mix in the polymer chain of growth with putting up with again, particularly pass through continuous polymerization.Though this method is used to prepare Alathon and multipolymer is more effective, not really effectively maybe can not be used at C 3-8The homopolymer of alpha-olefin or C 3-8Form long-chain branch in the multipolymer of alpha-olefin mixture.Use method for preparing EPDM multipolymer among the US-A-5 665 800, the melt flow rate (MFR) I10/I2 of described multipolymer is greater than 5.63, molecular weight distribution (Mw/Mn) is limited by following formula: Mw/Mn＜(I10/I2)-4.63, the critical shearing stress when overall melt fracture begins is greater than about 4 * 10 6Dynes/cm 2General hope increases long chain branching content in the olefin polymer, because the melt rheological property of resulting polymers improves.
The monomeric multipolymer of ethene and branched olefin is disclosed among the US-A-5 444 145.Unfriendly, prepare this multipolymer with above-mentioned technology and need use the more expensive alkene that contains desired preformed branched structure.This method is dumb, is not suitable for industrial application.Still need just to utilize (non-branching) olefinic monomer to form the method for the alpha-olefin copolymer product of long chain branching in the industry.The instruction that is comprised in above-mentioned patent, the open and U.S. Patent application of the same clan is incorporated herein for reference.
Summary of the invention
But the invention provides the preparation method of the homopolymer and the multipolymer of a kind of addition polymerization monomer or this monomeric mixture, described method comprises contacts described monomer or mixture with catalyst composition under the polymerizing condition of high monomer transformation efficiency, described catalyst composition comprises:
A) comprise the catalyst system of 3-10 family metal complexes; With
C) corresponding to the silane compound of following formula:
J jSiH 4-jOr A nJ jSiH 4-(n+j)
Wherein:
J is C 1-40Alkyl,
A is C 2-20Alkenyl,
N be 1 or 2 and
J is 0 or 1;
Wherein said polymkeric substance comprises 0.1 to 100 long-chain branch/10000 carbon, and at least some polymkeric substance comprise silane branching center.
Compare with the polymerization process of the similar catalyst composition that uses no above-mentioned silane branching agent, the long-chain branch of the inventive method produces efficient and is significantly improved.In addition, the inventive method can be used for being not suitable for mixing the monomer polymerization of β-hydride ion elimination products again, thereby can be contained the polymkeric substance of long chain branching first by this monomer preparation.Owing to contain a plurality of reactions position in the silane that alkenyl replaces, so realize that the required silane amount of branching that requires is little, depend on polymerizing condition, seldom surpass 5% weight of reaction mixture.The silane that uses excessive alkenyl to replace may cause forming crosslinked polymkeric substance.
Citation all about the periodic table of elements herein all refers to CRC publishing company, 1995 periodic table of elements of publishing.And, all are the families of in this periodic table of elements, reflecting with IUPAC meter family system or are all about family or the citation that is.
Be preferred for silane of the present invention or the hydrocarbyl si lanes branching agent comprises SiH 4, methyl-monosilane, ethylsilane, normal-butyl silane, octadecylsilane, phenyl silane and benzyl silane.The mixture of above-mentioned silane also can use.Though SiH 4For gas and be easy to add in the modern polymerization technique and remove from reaction mixture by devolatilization subsequently, but aryl-silane particularly phenyl silane or benzyl silane activity under polymerizing condition of the present invention are higher, thereby more effective in forming long-chain branch.
The silane branching agent that is preferred for alkenyl replacement of the present invention comprises vinyl silanes, 3-butenyl silane, 5-hexenyl silane, vinyl cyclohexene base silane, 7-octenyl silane, 17-vaccenic acid base silane, 3-butenyl methyl-monosilane, 7-octenyl ethylsilane, vinyl normal-butyl silane, 7-octenyl octadecylsilane, 3-butenyl phenyl silane and 7-octenyl benzyl silane.The mixture of above-mentioned silane also can use.Though it is undersaturated that described alkenyl silane is preferably end, the alkenyl silane such as the 6-octenyl silane of unsaturated link(age) also can be used as long chain branching agent of the present invention in containing.The alkenyl silane that is used to form novel polymer of the present invention obtains with silane addition reaction under condition known in this field that silane or alkyl replace by diolefine such as octadiene.
Term used herein " long chain branching " means lateral oligomeric alkyl and links to each other with polymer chain, and this group has 6 or more carbon but be not comonomer polymerization (for example propylene, 1-butylene, 1-hexene, 1-octene) or the branched olefin polymeric result who deliberately adds.Long chain branching comprises under the situation that relates to or do not relate to described silane and to mix the polymkeric substance side chain that is produced again because of remainder due to β-hydride ion cancellation process among the present invention.This long-chain branch also reflects the monomer difference that exists in the polymerization reactor, because they are a part of pre-polymerization polymkeric substance that mix in the polymer chain of growth on actual effect.
The technology that long chain branching degree in several measurement multipolymers has been arranged at present.Main analytical technology comprise based on 13Those that C NMR analyzes combine with little angle laser light scattering or similar granulometry technology alternatively.In addition, by with labeled monomer as being rich in 13The 1-octene of C or ethene preparation contrast multipolymer are supposed in the multipolymer that utilizes unmodified monomer to prepare under suitable condition to exist the side chain of par to distribute, and can assess short-chain branch, promptly because of rich C 3-8Side chain due to the comonomer remnants.Determine the long chain branching degree by subtraction then.In technology of the present invention, except that any traditional long chain branching due to the processing technology of above-mentioned continuous high conversion, also can be by the silane branching center that exists in the gained multipolymer (for example measuring) quantificational expression long chain branching degree by NMR.Preferred polymkeric substance contains 0.3 to 10 long-chain branch/10000 carbon according to the present invention.
Can improve the incidence of long chain branching by careful CONTROL PROCESS condition.For example, (wherein reactant and catalyzer add in the polymerization reactor continuous solution polymerization method that utilization is operated under the high conversion condition continuously, product is therefrom discharged continuously) help mixing of long-chain branch, because the monomeric relative volumetric molar concentration of the long-chain of the ethenyl blocking of Chan Shenging increases on the spot.In addition, cause the high processing condition of the partial concn of β-hydride ion elimination products for example gaseous polymerization also help forming long-chain branch.
In the inventive method and the product, some long-chain branchs relate to the result of the key of the Si-H in succession replacement(metathesis)reaction of the polymer chain of active catalyst center, growth and silane.This be need with interact at least three times iterative method of silane branching agent, can followingly represent:
Wherein (M) expression and the polymer chain of growth or the active catalyst position of hydrogen bonding, J such as front define.Resulting polymers contains silane-long chain branching center uniquely.Also can find out SiH in the above scheme 4Replacement(metathesis)reaction can take place in long chain branching agent again, produces three new substituted silane long-chain centers.Except that the present invention is realized the long chain branching, silane or hydrocarbyl si lanes branching agent also can influence polymerization technique, thereby cause polymericular weight to descend.
In addition, the unsaturated functional group of olefinic of the silane that alkenyl replaces further strengthens described long chain branching method, and it can become the part of main polymer chain or long-chain branch.The residue Si-H functional group's of the silane compound that this alkenyl replaces reaction as previously described.
But being applicable to that metal complexes of the present invention comprises can polymerization or be activated into any title complex of the periodic table of elements 3-10 family metal of the above-mentioned polyaddition compounds of polymerization (particularly alkene).Example comprises the 10th family's diimine derivative corresponding to following formula:
Wherein:
M* is Ni (II) or Pd (II);
X ' is halogen, alkyl or-oxyl;
A-is an aryl, particularly 2, and 6-diisopropyl phenyl or anilino;
The bivalent bridging group of described two nitrogen-atoms by maximum 60 non-hydrogen atoms particularly 1,2-second two bases, 2,3-fourth two bases, dimethylene silyl or condensed ring system are as 1, and 8-naphthalene two bases link to each other; With
A -Anionic group for above-mentioned ionization activator.
People such as M.Brookhart exist JACS, 118,267-268 (1996), Americanized Association's will, 117, people such as 6414-6415 (1995) and J.Feldman exist Organometallic chemistry, 1997,16, disclosing above-mentioned title complex among the 1514-1516 is active polymerizing catalyst, especially for the polymerization of alpha-olefin or the polymerization of alpha-olefin and polar comonomers such as vinylchlorid, alkyl acrylate and alkyl methacrylate.
Other title complex comprises the 3rd, 4 families that contain 1 to 3 π-key bonding negatively charged ion or neutral ligand base or the derivative of lanthanide series metal, and described part base can be ring or acyclic delocalization π-key bonding anion ligand base.The example of this π-key bonding anion ligand base is conjugation or unconjugated, ring or acyclic dialkylene, allyl group, the assorted phenyl of boron and aryl.Term " π-key bonding " means described part base by sharing electronics and the described transition metal bonding from part delocalized π-key.
The group that each atom in described delocalization π-key binding groups can be selected from the metalloid base of hydrogen, halogen, alkyl, halo alkyl, alkyl replacement independently replaces, wherein said metalloid is selected from the periodic table of elements the 14th family, and the metalloid base that this alkyl or alkyl replace is further contained the heteroatomic part of the 15th or 16 families and replaces.Term " alkyl " comprises C 1-20Straight chain, side chain and cyclic alkyl, C 6-20Aryl, C 7-20The aryl that alkyl replaces, and C 7-20The alkyl that aryl replaces.In addition, two or more this group can form the condensed ring system together, comprises partially or completely hydrogenant condensed ring system, and perhaps they can form metallic heterocyclic with described metal.The organic quasi-metal base that the alkyl that is suitable for replaces comprises one-, the organic quasi-metal base of two-and three-the 14th family's element of replacing, wherein each alkyl contains 1 to 20 carbon atom.The example of the organic quasi-metal base that the alkyl that is suitable for replaces is trimethyl silyl, triethylsilyl, ethyl dimetylsilyl, methyl diethylsilane base, triphenyl germyl and trimethylammonium germyl.The example that contains the 15th or 16 heteroatomic parts of family comprises amine, phosphine, ether or thioether part or its divalent derivative, for example with described transition metal or lanthanide series metal bonding and with described alkyl or contain amine, phosphine, ether or the thioether group that metalloid base key that alkyl replaces closes.
The example of the negatively charged ion delocalization π-key binding groups that is suitable for comprises cyclopentadienyl, indenyl, fluorenyl, tetrahydro indenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydro anthryl, six hydrogen anthryls, decahydro anthryl and boron mix phenyl and C thereof 1-10That alkyl replaces or C 1-10The derivative that the silyl that alkyl replaces replaces.Preferred anionic surfactants delocalization π-key binding groups is cyclopentadienyl, pentamethyl-cyclopentadienyl, tetramethyl-ring pentadienyl, tetramethyl-silyl cyclopentadienyl, indenyl, 2,3-dimethyl indenyl, fluorenyl, 2-methyl indenyl, 2-methyl-4-phenyl indenyl, tetrahydrofluorenyl, octahydrofluorenyl and tetrahydro indenyl.
The assorted benzene of boron is the boracic anion ligand that is similar to benzene.They are known in the art, and are described in people's such as G.Herberich Organometallic chemistry, 14,1, among the 471-480 (1995).The assorted benzene of preferred boron is corresponding to following formula:
R wherein " be selected from alkyl, silylation, N, N-dialkyl amido, N, N-ammonia diaryl base or germane base, described R " maximum 20 non-hydrogen atoms are arranged.In the title complex of the divalent derivative that comprises this delocalization π-key binding groups, thereby an one atom forms the bridging system by the divalent radical of covalent linkage or covalent bonding and another atomic linkage of described title complex.
The catalyzer that one class is suitable for is the transition metal complex corresponding to following formula:
K ' kMZ ' mL 1X p, or its dipolymer,
Wherein:
K ' is for containing the anion-radicals of K ' by the delocalization π-electronics of itself and M bonding, and described K ' contains maximum 50 non-hydrogen atoms, and two K ' bases link together and form bridged linkage alternatively, further alternatively K ' can with Z ' bonding;
M be in+2 ,+3 or+periodic table of elements group-4 metal of 4 apparent oxidation state;
Z ' is for optionally forming the divalent substituent of maximum 50 non-hydrogen atoms of metallic heterocyclic with K ' and M;
L is optional neutral ligand, and maximum 20 non-hydrogen atoms are arranged;
It when X occurs at every turn the univalent anion part of maximum 40 non-hydrogen atoms, alternatively two X each other covalent bonding be formed with two dianion parts with the valency of M bonding, perhaps alternatively two X each other covalent bonding form neutrality, conjugation or unconjugated diolefine (this moment, M was in+2 oxidation state) by delocalization π-electronics and M bonding, perhaps also alternatively one or more X and one or more L base each other bonding form all and pass through Lewis base functional group coordinate part with it with the merging of M covalent linkage;
K is 0,1 or 2;
M is 0 or 1;
L is 0 to 3 number;
P is 0 to 3 integer; With
The k+m+p sum equals the apparent oxidation state of M, but when two X bases formed neutrality by delocalization π-electronics and M bonding, conjugation or non-conjugated diene hydrocarbon together, the k+m sum equaled the apparent oxidation state of M.
Preferred complexes comprises those title complexs that contain one or two K ' base.Back one title complex comprises those title complexs that contain the bridging group that connects two K ' bases.Preferred bridging group be corresponding to formula (ER ' 2) xThose bridging groups, wherein E is silicon, germanium, tin or carbon, independently for hydrogen or be selected from the group of silylation, alkyl,-oxyl and combination thereof, it was 1 to 8 that described R ' has maximum 30 carbon or Siliciumatom and x when R ' occurred at every turn.Be methyl, ethyl, propyl group, benzyl, the tertiary butyl, phenyl, methoxyl group, oxyethyl group or phenoxy group when preferably, R ' occurs at every turn independently.
The described example that contains the title complex of two K ' bases is the compound corresponding to following formula:
Or
Wherein:
M is+2 ,+3 or+titanium, zirconium or the hafnium of 4 apparent oxidation state, preferred zirconium or hafnium;
R 3Be independently selected from alkyl, silylation, germane base, halogen, halo alkyl,-oxyl, silicon alkyl alcoxyl base, N when occurring at every turn, N-two (silicon alkyl alkyl) amino, N-alkyl-N-silylation amino, N, the alkyl that N-two (alkyl) is amino, alkylene is amino, two (alkyl) phosphino-, sulfenyl or-oxyl replace, described R 3Maximum 20 non-hydrogen atoms are arranged, perhaps adjacent R 3Thereby base form together divalent derivative form the condensed ring system and
X " is the anion ligand base of maximum 40 non-hydrogen atoms, perhaps two X independently at every turn " and forms the dianion part base of maximum 40 non-hydrogen atoms together when occurring,
When X occurs at every turn independently for being selected from 2-(N, N-dimethylamino) benzyl, m-(N, N-dimethylamino methyl) phenyl, allyl group and C 1-10The allylic stabilization anion ligand base that alkyl replaces, this moment, M was in+3 apparent oxidation state; Be the derivative of the neutral conjugation diene of maximum 40 non-hydrogen atoms or its silylation, germane base or the replacement of halo alkyl when perhaps X occurs at every turn independently, this moment, M was in+2 apparent oxidation state,
E is silicon, germanium, tin or carbon,
When R ' occurs at every turn independently for hydrogen or be selected from the group of silylation, alkyl,-oxyl and combination thereof, described R ' have maximum 30 carbon or Siliciumatom and
X is 1 to 8.
Above-mentioned metal complexes is particularly useful for making the polymkeric substance with stereospecific molecular structure.In this ability, preferably this title complex has C sSymmetry or chirality solid rigid structure is arranged.The example of the first kind is that the compound of different delocalization π-key ligands bound thereto base as a cyclopentadienyl and a fluorenyl arranged.People such as Ewen exist JACS, 110, the similar system that discloses among the 6255-6256 (1980) based on Ti (IV) or Zr (IV) is used to prepare the syndiotaxy olefin polymer.The example of chiral structure comprises the two indenyl title complexs of racemize.People such as Wild exist The organometallic chemistry periodical, 232, the similar system that discloses among the 233-47 (1982) based on Ti (IV) or Zr (IV) is used to prepare the isotaxy olefin polymer.
The example that contains the bridgingligand of two π-key bonding radical is: dimethyl-two (cyclopentadienyl) silicomethane, dimethyl-two (tetramethyl-ring pentadienyl) silicomethane, dimethyl-two (2-ethyl cyclopentadiene-1-yl) silicomethane, dimethyl-two (2-tertiary butyl cyclopentadiene-1-yl) silicomethane, 2, two (tetramethyl-ring pentadienyl) propane of 2-, dimethyl-two (indenes-1-yl) silicomethane, dimethyl-two (tetrahydroindene-1-yl) silicomethane, dimethyl-two (fluorenes-1-yl) silicomethane, dimethyl-two (tetrahydrochysene fluorenes-1-yl) silicomethane, dimethyl-two (2-methyl-4-phenylindan-1-yl) silicomethane, dimethyl-two (2-methyl indenes-1-yl) silicomethane, dimethyl (cyclopentadienyl) (fluorenes-1-yl) silicomethane, dimethyl (cyclopentadienyl) (octahydro fluorenes-1-yl) silicomethane, dimethyl (cyclopentadienyl) (tetrahydrochysene fluorenes-1-yl) silicomethane, (1,1,2, the 2-tetramethyl-)-1, two (cyclopentadienyl) silicoethanes of 2-, 1, two (cyclopentadienyl) ethane of 2-, and dimethyl (cyclopentadienyl)-1-(fluorenes-1-yl) methane.
" base is selected from hydride ion, alkyl, silylation, germane base, halo alkyl, halogenated silanes base, silylation alkyl and hydrocarbyl amino to preferred X, and perhaps " base forms divalent derivative to two X together." base is C to most preferred X 1-20Alkyl.
Preferred X base is 1,3-pentadiene and 1, the 4-diphenyl diethylene.
The another kind of formula K ' that is applicable to metal complexes of the present invention corresponding to the front kMZ ' mL 1X p, or its dipolymer, wherein Z ' is for forming the divalent substituent of maximum 50 non-hydrogen atoms of metallic heterocyclic with K ' and M.
Preferred divalence Z ' substituting group comprises the group that contains at least one atom that directly links to each other with K ' (for oxygen, sulphur, boron or the periodic table of elements the 14th family's element) and and not homoatomic maximum 30 non-hydrogen atoms that are selected from nitrogen, phosphorus, oxygen or sulphur of M covalent bonding.
Be preferred for a class group-4 metal coordinate complex of the present invention corresponding to following formula:
Figure C9980263100121
Or
Wherein:
M is titanium or zirconium;
R 3Be independently selected from alkyl, silylation, germane base, halogen, halo alkyl,-oxyl, silicon alkyl alcoxyl base, N when occurring at every turn, N-two (silicon alkyl alkyl) amino, N-alkyl-N-silylation amino, N, the alkyl that N-two (alkyl) is amino, alkylene is amino, two (alkyl) phosphino-, sulfenyl or-oxyl replace, described R 3Maximum 20 non-hydrogen atoms are arranged, perhaps adjacent R 3Thereby base forms divalent derivative together and forms the condensed ring system,
Each X is halogen, alkyl,-oxyl or silylation, and described group has maximum 20 non-hydrogen atoms, and perhaps two X bases form its divalent derivative together;
X has the neutral conjugation diene of maximum 40 non-hydrogen atoms or the derivative that its silylation, germane base or halo alkyl replace, and this moment, M was in+2 apparent oxidation state,
Y is-O-,-S-,-NR '-or-PR '-; With
Z is SiR ' 2, CR ' 2, SiR ' 2SiR ' 2, CR ' 2CR ' 2, CR '=CR ', CR ' 2SiR ' 2, or GeR ' 2, be hydrogen or the group that is selected from silylation, alkyl,-oxyl and combination thereof independently when wherein R ' occurs at every turn, described R ' has maximum 30 carbon or Siliciumatom.
Another kind of suitable title complex is corresponding to following formula:
Figure C9980263100131
Wherein:
M is titanium or zirconium, preferably is in+titanium of 3 apparent oxidation state;
R 3Be independently selected from alkyl, silylation, germane base, halogen, halo alkyl,-oxyl, silicon alkyl alcoxyl base, N when occurring at every turn, N-two (silicon alkyl alkyl) amino, N-alkyl-N-silylation amino, N, the alkyl that N-two (alkyl) is amino, alkylene is amino, two (alkyl) phosphino-, sulfenyl or-oxyl replace, described R 3Maximum 20 non-hydrogen atoms are arranged, perhaps adjacent R 3Thereby base forms divalent derivative together and forms the condensed ring system,
Each X is halogen, alkyl,-oxyl or silylation, and described group has maximum 20 non-hydrogen atoms, and perhaps two X bases form its divalent derivative together;
E is silicon, germanium, tin or carbon,
Be hydrogen or the group that is selected from silylation, alkyl,-oxyl and combination thereof independently when R ' occurs at every turn, described R ' has maximum 30 carbon or Siliciumatom,
X is 1 to 8,
Y is-OR or-NR 2With
Z is SiR ' 2, CR ' 2, SiR ' 2SiR ' 2, CR ' 2CR ' 2, CR '=CR ', CR ' 2SiR ' or GeR ' 2, wherein R ' defines as the front.
Another kind of suitable title complex is corresponding to following formula:
Wherein:
M is titanium or zirconium, preferably is in+titanium of 3 apparent oxidation state;
R 3Be independently selected from alkyl, silylation, germane base, halogen, halo alkyl,-oxyl, silicon alkyl alcoxyl base, N when occurring at every turn, N-two (silicon alkyl alkyl) amino, N-alkyl-N-silylation amino, N, the alkyl that N-two (alkyl) is amino, alkylene is amino, two (alkyl) phosphino-, sulfenyl or-oxyl replace, described R 3Maximum 20 non-hydrogen atoms are arranged, perhaps adjacent R 3Thereby base forms divalent derivative together and forms the condensed ring system,
X " " be 2-(N, N-dimethylamino) benzyl, m-(N, N-dimethyl aminomethyl) phenyl, allyl group or C 1-10The allyl group that alkyl replaces;
Y is-O-,-S-,-NR '-or-PR '-; With
Z is SiR ' 2, CR ' 2, SiR ' 2SiR ' 2, CR ' 2CR ' 2, CR '=CR ', CR ' 2SiR ' 2, or GeR ' 2, wherein R ' defines as the front.
The illustrative example that can be used for implementing group-4 metal complexes of the present invention comprises:
The bicyclic pentadiene title complex as:
Dichloro two (cyclopentadienyls) close zirconium,
Dimethyl two (cyclopentadienyls) close zirconium,
Dichloro two (tertiary butyl cyclopentadienyls) close zirconium,
Dimethyl two (tertiary butyl cyclopentadienyls) close zirconium,
Dichloro (fluorenyl) (cyclopentadienyl) close zirconium,
Dimethyl (fluorenyl) (cyclopentadienyl) close zirconium,
Dichloro two (indenyls) close zirconium,
Dimethyl two (indenyls) close zirconium,
Dichloro racemize-dimethylsilane-two (cyclopentadienyl) close zirconium,
Dimethyl racemize-dimethylsilane-two (cyclopentadienyl) close zirconium,
Dichloro racemize-dimethylsilane-two (tetramethyl-ring pentadienyl) close zirconium,
Dimethyl racemize-dimethylsilane-two (tetramethyl-ring pentadienyl) close zirconium,
Dichloro racemize-dimethylsilane-two { 1-(2-methyl-4-phenyl indenyl) } close zirconium,
Dichloro racemize-dimethylsilane-two { 1-(2-methyl-4-(Alpha-Naphthyl) indenyl) } close zirconium,
Dichloro racemize-dimethylsilane-two { 1-(2-methyl-4-(betanaphthyl) indenyl) } close zirconium,
Dichloro racemize-ethylene-two { 1-(2-methyl-4-phenyl indenyl) } close zirconium,
Dichloro racemize-ethylene-two { 1-(2-methyl-4-(Alpha-Naphthyl) indenyl) } close zirconium,
1,4-phenylbenzene-1,3-butadiene racemize-dimethylsilane-two (cyclopentadienyls) close zirconium (II),
2,4-hexadiene racemize-dimethylsilane-two (cyclopentadienyls) close zirconium (II),
1,3-pentadiene racemize-dimethylsilane-two { 1-(2-methyl-4-phenyl indenyl) } close zirconium (II),
1,3-pentadiene racemize-dimethylsilane-two { 1-(2-methyl-4-(Alpha-Naphthyl) indenyl) } close zirconium (II),
1,3-pentadiene racemize-ethylene-two { 1-(2-methyl-4-phenyl indenyl) } close zirconium (II),
1,3-pentadiene racemize-ethylene-two { 1-(2-methyl-4-(Alpha-Naphthyl) indenyl) } close zirconium (II),
1,3-pentadiene racemize-ethylene-two { 1-(2-methyl-4-(betanaphthyl) indenyl) } close zirconium (II),
1,3-pentadiene racemize-ethylene-two { 1-(2-methyl-4-(1-anthryl) indenyl) } close zirconium (II),
1,3-pentadiene racemize-ethylene-two { 1-(2-methyl-4-(2-anthryl) indenyl) } close zirconium (II),
1,3-pentadiene racemize-ethylene-two { 1-(2-methyl-4-(9-anthryl) indenyl) } close zirconium (II),
1,3-pentadiene racemize-ethylene-two { 1-(2-methyl-4-(9-phenanthryl) indenyl) } close zirconium (II),
1,4-phenylbenzene-1,3-butadiene racemize-ethylene-two { 1-(2-methyl-4-phenyl indenyl) } close zirconium (II),
1,4-phenylbenzene-1,3-butadiene racemize-ethylene-two { 1-(2-methyl-4-(Alpha-Naphthyl) indenyl) } close zirconium (II) and
1,4-phenylbenzene-1,3-butadiene racemize-ethylene-two { 1-(2-methyl-4-(betanaphthyl) indenyl) } closes zirconium (II).
Be used for wherein metal of the present invention to be in+the containing delocalization π-electronics and comprise following title complex of 4 apparent oxidation state with the example of the metal complexes (being called limited title complex how much) of the monocycle part of bridged linkage:
Dichloro (uncle's fourth amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
Dichloro (hexamethylene amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
Dichloro (cyclododecane amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
Dichloro (uncle's fourth amino) (2-methyl-4-phenylindan-1-yl) dimethylsilane close titanium,
Dichloro (uncle's fourth amino) (3-pyrryl indenes-1-yl) dimethylsilane close titanium,
Dichloro (hexamethylene amino) (3-pyrryl indenes-1-yl) dimethylsilane close titanium,
Dichloro (uncle's fourth amino) (η 5-3-phenyl-s-cyclopenta indenes (indacen)-1-yl) dimethylsilane close titanium,
Dichloro (uncle's fourth amino) (η 5-2-methyl-3-xenyl-s-cyclopenta indenes-1-yl) dimethylsilane close titanium,
Dichloro (uncle's fourth amino) (η 5-3-phenyl-together with the dimethylsilane of-dimethyl acenaphthene-1-yl) close titanium,
Dimethyl (uncle's fourth amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
Dimethyl (hexamethylene amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
Dimethyl (cyclododecane amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
Dimethyl (uncle's fourth amino) (2-methyl-4-phenylindan-1-yl) dimethylsilane close titanium,
Dimethyl (uncle's fourth amino) (3-pyrryl indenes-1-yl) dimethylsilane close titanium,
Dimethyl (hexamethylene amino) (3-pyrryl indenes-1-yl) dimethylsilane close titanium,
Dimethyl (uncle's fourth amino) (η 5-3-phenyl-s-cyclopenta indenes-1-yl) dimethylsilane close titanium,
Dimethyl (uncle's fourth amino) (η 5-2-methyl-3-xenyl-s-cyclopenta indenes-1-yl) dimethylsilane close titanium,
Dimethyl (uncle's fourth amino) (η 5-3-phenyl-together with the dimethylsilane of-dimethyl acenaphthene-1-yl) close titanium,
1,4-phenylbenzene-1,3-butadiene (uncle's fourth amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
1,4-phenylbenzene-1,3-butadiene (hexamethylene amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
1,4-phenylbenzene-1,3-butadiene (cyclododecane amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
1,4-phenylbenzene-1,3-butadiene (uncle's fourth amino) (2-methyl-4-phenylindan-1-yl) dimethylsilane close titanium,
1,4-phenylbenzene-1,3-butadiene (uncle's fourth amino) (3-pyrryl indenes-1-yl) dimethylsilane close titanium,
1,4-phenylbenzene-1,3-butadiene (hexamethylene amino) (3-pyrryl indenes-1-yl) dimethylsilane close titanium,
1,4-phenylbenzene-1,3-butadiene (uncle's fourth amino) (η 5-3-phenyl-s-cyclopenta indenes-1-yl) dimethylsilane close titanium,
1,4-phenylbenzene-1,3-butadiene (uncle's fourth amino) (η 5-2-methyl-3-xenyl--s-cyclopenta indenes-1-yl) dimethylsilane close titanium,
1,4-phenylbenzene-1,3-butadiene (uncle's fourth amino) (η 5-3-phenyl-together with the dimethylsilane of-dimethyl acenaphthene-1-yl) close titanium,
1,3-pentadiene (uncle's fourth amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
1,3-pentadiene (hexamethylene amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
1,3-pentadiene (cyclododecane amino) (tetramethyl-ring pentadienyl) dimethylsilane close titanium,
1,3-pentadiene (uncle's fourth amino) (2-methyl-4-phenylindan-1-yl) dimethylsilane close titanium,
1,3-pentadiene (uncle's fourth amino) (3-pyrryl indenes-1-yl) dimethylsilane close titanium,
1,3-pentadiene (hexamethylene amino) (3-pyrryl indenes-1-yl) dimethylsilane close titanium,
1,3-pentadiene (uncle's fourth amino) (η 5-3-phenyl-s-cyclopenta indenes-1-yl) dimethylsilane close titanium and
1,3-pentadiene (uncle's fourth amino) (η 5-2-methyl-3-xenyl-s-cyclopenta indenes-1-yl) dimethylsilane closes titanium.
Other title complex, those title complexs that particularly contain other group-4 metal it will be apparent to those skilled in the art that.
By making up with active cocatalyst or utilizing activating technology to make described preferred group-4 metal complexes give catalytic activity.The active cocatalyst that is applicable to this paper comprises the aikyiaiurnirsoxan beta of methylaluminoxane, diisobutyl alumina alkane or the modification of perfluor aryl of polymeric or oligomeric aikyiaiurnirsoxan beta, particularly methylaluminoxane, triisobutyl aluminium-modification; Strong lewis acid is as C 1-30The 13rd compounds of group, particularly three (alkyl) aluminium that alkyl replaces-or three (alkyl) boron-compound and halo derivatives thereof, 1 to 10 carbon atom is arranged, particularly three (pentafluorophenyl group) borine in each alkyl or the halo alkyl; With non-polymeric, inert, compatible, non-coordinate, generation ionic compound (be included in and use these compounds under the oxidizing condition).The activating technology that is suitable for is bulk electrolysis (back will be explained in detail).Also can adopt the combination of above-mentioned active cocatalyst and technology as needs.Above-mentioned active cocatalyst is instructed at different metal complexess in below with reference to document with activating technology: EP-A-277 003; US-A-5 153 157; US-A-5 064 802; EP-A-468 651; EP-A-520732; With WO 93/23412; These documents all are incorporated herein for reference.
During use, suitable polymerization or oligomeric aikyiaiurnirsoxan beta exist with 10: 1 to 1000: 1, preferred 50: 1 to 200: 1 molar weight with respect to metal complexes.It is generally acknowledged that aikyiaiurnirsoxan beta or alkylaluminoxane are oligomeric or polymeric aluminum alkyls oxygen compound, comprise cyclic oligomer.This compound generally contains average about 1.5 alkyl/aluminium atom, by trialkyl aluminium compound or its mixture and water prepared in reaction.The aikyiaiurnirsoxan beta that the perfluor aryl replaces be easy to by alkylaluminoxane (trialkyl aluminium compound that also may contain surplus) with fluorinated aryl ligand sources (strong lewis acid that preferably contains the fluoro aromatic ligand) chemical combination, remove the by product that ligand exchange generates then and prepare.Preferred fluorinated aryl ligand sources is three fluoro aryl boron compounds, three (pentafluorophenyl group) boron most preferably, and its produces more volatile and the easy trialkylboron ligand exchange product of removing from reaction mixture.
This reaction can be carried out in any aliphatic series, alicyclic or aromatics liquid diluent or its mixture.Preferred C 6-8Aliphatic series and clicyclic hydrocarbon and composition thereof comprise hexane, heptane, hexanaphthene and mixed fraction such as Isopar TME (available from Exxon chemical company).Alkylaluminoxane is with after the fluorinated aryl ligand sources contacts, can make reaction mixture by any suitable technology purifying to remove the ligand exchange product, particularly any trialkylboron compound.Perhaps, can be earlier with described 3-10 family's metal complex catalysts and this reaction mixture before removing remaining ligand exchange product.
Being applicable to that the technology of removing alkyl exchange by product from reaction mixture comprises alternatively under reduced pressure outgases, distillation, exchange of solvent, solvent extraction, contacts with the volatile reagent extraction, with zeolite or molecular sieve and the combination of above-mentioned technology, and all these technology are all carried out according to a conventional method.The purity of products obtained therefrom can be passed through products obtained therefrom 13B NMR measures.Preferably, the amount that exchanges product by solid content residue alkyl is lower than 10% weight, preferably is lower than 1.0% weight, most preferably is lower than 0.1% weight.
Be adapted in the one embodiment of this invention non-polymeric, the inert as promotor, compatible, non-coordinate, generation ionic compound and comprise a positively charged ion (it is the Bronsted acid that proton can be provided) and a compatible non-coordinate negatively charged ion A-.Preferred anionic surfactants is those negatively charged ion that contain single coordinate complex, and described title complex comprises charged metal or metalloid core, the electric charge of the deactivated catalyst part (metallic cation) that this negatively charged ion generates when can balance two components mixing.And described negatively charged ion can be by olefinic, diolefinic and acetylenically unsaturated compound or other neutral Lewis base such as ether or nitrile displacement.The metal that is fit to includes but not limited to aluminium, gold and platinum.The metalloid that is fit to includes but not limited to boron, phosphorus and silicon.It is known containing the anionic compound that comprises the coordinate complex that contains single metal or metalloid atom, many commercially available, and this compound that particularly contains single boron atom in the anionicsite is commercially available.
Preferably, this promotor can be represented by following general formula:
(L*-H) + dA d-
Wherein:
L* is a neutral Lewis base;
(L*-H) +Be Bronsted acid;
A D-Be non-coordinate, compatible negatively charged ion, have electric charge d-and
D is 1 to 3 integer.
More preferably d is 1, i.e. A D-Be A -
Preferred especially A -Corresponding to following formula: [BQ 4] -
Wherein:
B is the boron of+3 apparent oxidation state; With
Q is independently selected from hydride ion, dialkylamino, halogen ion, pure radical ion, aryloxy, alkyl, halocarbon base (halocarbyl) and halo alkyl at every turn when occurring, described Q has maximum 20 carbon, and condition is that Q is that halogen ionic situation is once no more than.
In a more preferred embodiment, Q is fluoro C 1-20Alkyl, most preferably fluorinated aryl, particularly pentafluorophenyl group.
Can in Preparation of Catalyst of the present invention, be used as the illustrative of the cationic generation ionic compound that proton can be provided comprising of active cocatalyst and non-limitative example is:
Trisubstituted ammonium salt as:
Tetraphenyl boric acid TMA (TriMethylAmine),
Tetraphenyl boric acid methyl two (octadecyl) ammonium,
Tetraphenyl boron triethylenetetraminehexaacetic acid ammonium,
Tetraphenyl boric acid 3 third ammoniums,
Tetraphenyl boric acid three positive fourth ammoniums,
Tetraphenyl boric acid methyl tetradecyl octadecyl ammonium,
Tetraphenyl boric acid 3,5-dimethylphenyl ammonium,
Tetraphenyl boric acid diethyl phenyl ammonium,
Tetraphenyl boric acid dimethyl (2,4, the 6-trimethylphenyl) ammonium,
Four (pentafluorophenyl group) boric acid TMA (TriMethylAmine),
Four (pentafluorophenyl group) boric acid methyl two (tetradecyl) ammonium,
Four (pentafluorophenyl group) boric acid methyl two (octadecyl) ammonium,
Four (pentafluorophenyl group) boron triethylenetetraminehexaacetic acid ammonium,
Four (pentafluorophenyl group) boric acid, 3 third ammoniums,
Four (pentafluorophenyl group) boric acid, three positive fourth ammoniums,
Four (pentafluorophenyl group) boric acid, three Zhong Ding ammoniums,
Four (pentafluorophenyl group) boric acid 3,5-dimethylphenyl ammonium,
Four (pentafluorophenyl group) boric acid diethyl phenyl ammonium,
Four (pentafluorophenyl group) boric acid dimethyl (2,4, the 6-trimethylphenyl) ammonium,
Four (2,3,4,6-tetrafluoro phenyl) boric acid TMA (TriMethylAmine),
Four (2,3,4,6-tetrafluoro phenyl) boron triethylenetetraminehexaacetic acid ammonium,
Four (2,3,4,6-tetrafluoro phenyl) boric acid 3 third ammoniums,
Four (2,3,4,6-tetrafluoro phenyl) boric acid three positive fourth ammoniums,
Four (2,3,4,6-tetrafluoro phenyl) boric acid dimethyl tertiary butyl ammonium,
Four (2,3,4,6-tetrafluoro phenyl) boric acid 3,5-dimethylphenyl ammonium,
Four (2,3,4,6-tetrafluoro phenyl) boric acid diethyl phenyl ammoniums and
Four (2,3,4,6-tetrafluoro phenyl) boric acid dimethyl (2,4, the 6-trimethylphenyl) ammoniums;
Dialkyl ammonium salt as:
Four (pentafluorophenyl group) boric acid two (octadecyl) ammonium,
Four (pentafluorophenyl group) boric acid, two (tetradecyl) ammoniums and
Four (pentafluorophenyl group) boric acid dicyclohexyl ammonium;
Three replace the De phosphonium salts as:
Four (pentafluorophenyl group) boric acid triphenyl phosphonium,
Four (pentafluorophenyl group) boric acid methyl two (octadecyl) Phosphonium and
Four (pentafluorophenyl group) boric acid three (2,6-xylyl) Phosphonium.
Preferred chain alkyl one-and dibasic ammonium title complex (C particularly 14-C 20The alkylammonium title complex) four (pentafluorophenyl group) borate, particularly four (pentafluorophenyl group) boric acid methyl two (octadecyl) ammoniums and four (pentafluorophenyl group) boric acid methyl two (tetradecyl) ammonium, and comprise its mixture.This mixture comprises by containing two C 14, C 16Or C 18The protonated ammonium cation of amine deutero-of an alkyl and a methyl.This amine can trade(brand)name Kemamine TMT9701 is available from Witco company with trade(brand)name Armeen TMM2HT is available from Akzo-Nobel company.
The another kind of generation ionic active cocatalyst that is suitable for comprises the compatible anionic salt with non-coordinate of a kind of cation oxidant, is expressed from the next:
(Ox e+) d(A d-) e
Wherein:
Ox E+For the cation oxidant of electric charge e+ is arranged;
E is 1 to 3 integer; With
A D-Define with d such as front.
The example of cation oxidant comprises: ferrocene, Ag that ferrocene (ferrocenium), alkyl replace +, or Pb + 2A D-Preferred version be the front about defined those negatively charged ion of the active cocatalyst that contains Bronsted acid, four (pentafluorophenyl group) borate particularly.
The another kind of generation ionic active cocatalyst that is suitable for comprises a kind of carbon ion or the compatible anionic salt with non-coordinate of silicon ion, is expressed from the next:
+A -
Wherein:
+Be C 1-20Carbon ion or silicon ion; With
A -Define as the front.
Preferred carbon ion is trityl positively charged ion, i.e. triphenylcarbenium.Preferred silicon ion is a triphenyl silicon.
The activating technology of bulk electrolysis relates to the electrochemical oxidation of metal complexes in the presence of the supporting electrolyte that is comprising non-coordination inert anion under electrolytic condition.In this technology, be used for such the use consequently of electrolytic solvent, supporting electrolyte and electrolytic potential and do not generate the electrolysis by product that makes metal complexes lose catalytic activity basically between the reaction period.More specifically, the solvent of Shi Heing is to be liquid state down, can to dissolve supporting electrolyte and inert material at electrolytic condition (general temperature is at 0 to 100 ℃)." inert solvent " is not to be reduced under the used reaction conditions of electrolysis or the solvent of oxidation.In view of the electrolytic reaction that requires, generally can select the solvent and the supporting electrolyte that not influenced by the used electrolytic potential of desired electrolysis.Preferred solvent comprise phenyl-difluoride (all isomer), DME, and composition thereof.
This electrolysis can be carried out in the standard electrolytic groove that anode and negative electrode (also being called working electrode and counter electrode) is housed.The material that is applicable to the structure electrolyzer is the metal of glass, plastics, pottery and glass coating.Electrode is prepared by inactive, conductive material, and 'inertia' means the electro-conductive material that not influenced by reaction mixture or reaction conditions.Platinum or palladium are preferred inactive, conductive material.Usually, ion permeable membrane such as thin frit are separated into chamber-working electrode chamber and counter electrode chamber separately with electrolyzer.Working electrode immerses in the reaction medium, and reaction medium comprises metal complexes, solvent, the supporting electrolyte that will be activated and is used to make the electrolysis mitigation or stablizes required any other material of gained title complex.Counter electrode is dipped in the mixture of solvent and supporting electrolyte.Can determine required voltage as the cleaning of the silver electrode in the ionogen that is dipped in electrolyzer electrolytic tank by Theoretical Calculation or with reference electrode.Also determine the background current of electrolyzer, i.e. electric current under no desired electrolytic situation.When electric current electrolysis when the level that requires is reduced to the background current level is finished.In this way, can easily detect the conversion fully of original metal title complex.
The supporting electrolyte that is fit to is to comprise the compatible non-coordination anion A with inertia of positively charged ion -Salt.Preferred supporting electrolyte is the salt corresponding to following formula:
G +A -；
Wherein:
G +For not with the positively charged ion of initial title complex and gained title complex reaction and
A -Be the compatible negatively charged ion of non-coordinate.
Positively charged ion G +Example comprise the An Huo phosphonium cation that tetraalkyl that 40 non-hydrogen atoms are arranged at most replaces.Preferred cation is four positive fourth ammonium cations.
During bulk electrolysis activation title complex of the present invention, the positively charged ion of supporting electrolyte feeds counter electrode, and A migrates to the negatively charged ion that working electrode becomes the gained oxidation products.The positively charged ion of solvent or supporting electrolyte is in the molar weight reduction to equate with the amount of the oxidized metal title complex that generates on the working electrode on the counter electrode.Preferred supporting electrolyte is the tetraalkyl ammonium salt of four (perfluor aryl) boric acid, 1 to 10 carbon is arranged, particularly four (pentafluorophenyl group) boric acid, four positive fourth ammoniums in each alkyl.
Usually, can by in the solvent that is fit under 100 ℃ to 300 ℃ temperature hybrid metal title complex and activator prepare described active catalyst.Silane or hydrocarbyl si lanes auxiliary agent can add dividually or simultaneously with all the other components.Catalyst composition can prepare by mixing the independent preparation of each component or wanting to mix in the presence of the polymeric monomer each component before the polymeric monomer is wanted in adding on the spot.The component of catalyzer is all very sensitive to moisture and oxygen, should operate in inert atmosphere and shift.
Be preferred for that monomer of the present invention includes 2 to 20000, alkene preferred 2 to 20, more preferably 2 to 8 carbon atoms and two or the mixture of multiple this alkene.The alkene of particularly suitable comprises: ethene, propylene, 1-butylene, 1-amylene, 4-methylpentene-1,1-hexene, 1-heptene, c octene, 1-nonene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes or its mixture, and the oligopolymer of the long-chain ethenyl blocking that generates between polymerization period or polymeric reaction product and add C in the reaction mixture specially in resulting polymers, producing than long-chain branch 10-30Alpha-olefin.Preferably, described alkene is vinylbenzene and the tetrafluoroethylene that ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene, vinylbenzene, halo or alkyl replace.Other monomer that is suitable for comprises vinyl cyclobutene and diolefine as 1,4-hexadiene, Dicyclopentadiene (DCPD), ethylidene norbornene and 1,7-octadiene.Above-mentioned monomeric mixture also can use.
Be applicable to that solvent or thinner in this Preparation of Catalyst comprise any solvent well known in the prior art, include but not limited to straight chain and branched-chain hydrocarbon such as C 6-12Paraffinic hydrocarbons (pentane, hexane, heptane, octane and composition thereof); C 6-12Ring and clicyclic hydrocarbon such as hexanaphthene, suberane, methylcyclohexane, methyl suberane and composition thereof; And C 6-12Aromatic substance that aromatics and alkyl replace such as benzene,toluene,xylene, naphthalane, and composition thereof, and the mixture of above-claimed cpd.
Described polymerization can be carried out under other reaction conditions that is fit to of slurry, solution, body, gas phase or suspension polymerization conditioned disjunction.This polymerization can be carried out the sufficiently long time to produce the polymkeric substance that requires under 0 to 160 ℃, preferred 25 to 100 ℃ temperature.The typical reaction times is 1 minute to 100 hours, preferred 1 to 10 hour.Optimum reacting time or reactor residence time will change with used temperature, solvent and other reaction conditions.Can carry out polymerization being lower than a normal atmosphere and surpassing under the normal atmosphere, be adapted at carrying out polymerization under the pressure of 1 to 500psig (6.9kPa-3400kPa).Consider that investment and equipment cost are lower, preferably adopt environment or low pressure, for example 1-5psig (6.9-34.5kPa).
Can be under the situation that has inert diluent or solvent or do not exist inert diluent or solvent promptly to exist under the situation of excess monomer to carry out polymerization.The thinner that is fit to or the example of solvent comprise C 6-20Aliphatic series, cyclic aliphatic, aromatics and halogenated aliphatic or aromatic hydrocarbon and composition thereof.Preferable absorbent comprises C 6-10Paraffinic hydrocarbons, toluene and composition thereof.Special ideal thinner is octane-iso, isononane or its blend such as Isopar-E TM(available from Exxon chemical company).Using proper amount of solvent to make monomer concentration is 5 to 100% weight.
But the mol ratio of addition polymerization monomer and catalyzer (by 3-10 family metal content) can be at 100: 1 to 1 * 10 10: in 1 the scope, preferred 1000: 1 to 1 * 10 6: 1.Typically in the preparation ethylene/olefin interpolymers, the mol ratio of used comonomer and monomer depends on the density that requires of the composition that will produce in the polymerization, is about 0.5 or lower.Ideally, production density is when about 0.91 material to about 0.93 scope, and the ratio of comonomer and monomer is lower than 0.2, preferably be lower than 0.05 even more preferably less than 0.02 even can be lower than 0.01.Typically, in this method the mol ratio of hydrogen and monomer be lower than about 0.5, preferably be lower than 0.2, more preferably less than 0.05 even more preferably less than 0.02 because there is the silane branching agent, it has finished the many functions of hydrogen aspect molecular weight control.That the mol ratio of silane in the reactor or hydrocarbyl si lanes branching agent and monomer of packing into is lower than ideally is about 0.5, preferably be lower than 0.2, more preferably less than 0.1.
As other similar polymerization, wish that very used monomer and solvent purity are enough high so that the catalyst deactivation phenomenon not to take place.Can adopt any suitable monomer purifying technology as devolatilization under reduced pressure, contact, outgas or its combination with molecular sieve or high surface area alumina.
May wish that also the purifying resulting polymers is to remove the catalyzer and the promotor of deentrainment.Surplus ash (being attributable to the metal value of catalyzer or promotor) during generally by the polymkeric substance pyrolysis is identified this pollutent.Be applicable to that the technology of removing this compound is by solvent extraction, for example high boiling chlorinated solvent, acid or alkali such as the caustic alkali with heat extracts, and filters then.
In catalyst formulation, particularly there is carrier alternatively in the catalyst formulation in gas phase or slurry phase polymerisation.The carrier that is fit to comprises any inert particulate material, but optimal be metal oxide, preferred aluminum oxide, silica or alumino-silicate materials.The granularity that is fit to is 1 to 1000 μ M, preferred 10 to 100 μ M.Optimal carrier is baked silica, can be by reducing surface hydroxyl with silane or similar reactive compounds reaction.Can adopt anyly to be applicable to the means that in catalyst formulation, comprise carrier, as component is scattered in the liquid as described in making, and contacts with carrier, dry then; With this spouting of liquid or be coated with described carrier, remove liquid then; Or make the co-precipitation from liquid medium of promotor and solid support material.
Carry out polymerization in the successive polymerization mode ideally, wherein catalyst component, monomer, chain branching agent and optional solvent and diolefine infeed reaction zone continuously, and therefrom discharge polymeric articles continuously.Comprise that in the scope of term used herein " continuously " and " continuously " the closely-spaced reactant that adds off and on rule is the successive process with taking out the consequently total process of product.
In one operation scheme, in the continuous solution polymerization system that comprises two reactors that serial or parallel connection connects, carry out polymerization.In a reactor, form product of higher molecular weight (Mw is 300000 to 600000, more preferably 400000 to 500000), and produce the product (Mw is 50000 to 300000) of lower molecular weight in second reactor.Final product is the blend of two reactor effluents, and they mixed the even blend that produces two kinds of polymeric articles before devolatilization.This double-reactor method can prepare the product that improves performance.In preferred embodiments, reactors in series connects, and promptly the effluent of first reactor adds second reactor, and adds new monomer, solvent and hydrogen in second reactor.It is 20: 80 to 80: 20 that conditioned reaction device condition makes the weight ratio of the polymkeric substance that produces in the polymkeric substance that produces in first reactor and second reactor.In addition, control the temperature of second reactor to produce the product of lower molecular weight.This system helps producing mooney viscosity and intensity and the fabulous EPDM product of processibility on a large scale.The preferred mooney viscosity (ASTM D1646-94, ML1+4@125 ℃) of regulating products obtained therefrom falls into 1 to 200, in preferred 5 to 150, most preferably 10 to 110 the scope.
Polymerization process of the present invention also can be advantageously used in the gas-phase copolymerization of alkene.This method is used to produce high density polyethylene(HDPE) (HDPE), medium-density polyethylene (MDPE), LLDPE (LLDPE) and polypropylene on a large scale industrial.Used vapor phase process can be for example to adopt mechanical stirring bed or gas fluidized bed as the polymerization zone type.Preferably in comprising the vertical round shape polymerization reactor that supports or be suspended in the polymer beads fluidized-bed on the orifice plate (fluidization grid), carry out the polymerization process of polyreaction.
Gases used comprising wanted the polymeric monomer by this bed of fluidisation, and this gas is also removed reaction heat as heat exchange medium from this bed.Hot gas is discharged from reactor head, passes through the stable region (be also referred to as reduction of speed district) of diameter than fluidisation bedside usually, and the particulate of being carried secretly in the air-flow has an opportunity to sink to returning in the bed therein.It also may be favourable removing ultra-fine grain with cyclonic separator from hot gas flow.Usually make gas circulation return described fluidized-bed with gas blower or compressor with one or more interchanger that from gas, proposes heat of polymerization then.
Except that being provided the cooling by described refrigerative circulation gas, making a refrigerative preferred method is to add volatile liquid so that heatcooling effect to be provided in bed, is commonly referred to condensing mode and operates.Used in the case volatile liquid can be a volatile inert liquid for example, as has an appointment 3 to stable hydrocarbon about 8, preferred 4 to 6 carbon atoms.Monomer or comonomer this as volatile liquid or can be condensed and provide under the situation of this liquid, be fit to it is added in the bed heatcooling effect will be provided.The example of the olefinic monomer that can use in this way is to contain about 3 to alkene about 8, preferred 3 to 6 carbon atoms.Volatile liquid evaporates in hot fluidized-bed and forms gas, mixes with fluidized gas.If volatile liquid is monomer or comonomer, it will experience some polymerizations in bed.Evaporated liquid is left reactor as the part of thermal cycling gas then, enters the compression/heat exchange section of circulation loop.Circulation gas cools off in interchanger, if the temperature that this gas is cooled is lower than dew point, then liquid will be separated out from gas.Ideally this liquid is circulated to fluidized-bed continuously.The liquid of being separated out can be looped back this bed with the drop form that is stated from the circulating current.These class methods are described in for example EP-89691; US4 543 399; Among WO-94/25495 and the US5 352 749.The particularly preferred method that liquid circulation is returned this is to isolate liquid from circulating current, again this liquid is directly injected this bed, preferably utilizes and produce the method that liquid carefully drips in bed.These class methods are described among the WO-94/28032.These documents are incorporated herein for reference.
The polyreaction that takes place in gas fluidized bed is by the catalyst of continuous or semicontinuous interpolation.This catalyzer can be carried on inorganic as mentioned above or the organic support material.Also can make this catalyzer through prepolymerization step, for example polymerization small amounts of olefins monomer in inert liquid diluent provides and contains the catalyst composite that is embedded in the granules of catalyst in the olefin polymer particle.
Directly in fluidized-bed, produce polymkeric substance by catalyzed copolymerization on the fluidized particles of monomer and catalyzer, loaded catalyst or the prepolymer of one or more comonomer in fluidized-bed.Utilize prefabricated bed of polymer particles, preferred class is similar to target polyolefins, in adding catalyzer, monomer and circulating current, require any other gas that has such as carrier gas, hydrogen chain-transfer agent or the condensable indifferent gas when operating in the vapor condensation mode before regulate this bed with rare gas element or nitrogen drying, the startup polyreaction.The polymkeric substance that produces is discharged from fluidized-bed on demand continuously or off and on.
Being best suited for and implementing vapor phase process of the present invention is continuous processing, wherein reactant is provided and discharges product from the reaction zone of reactor to the reaction zone of reactor continuously, thereby produce the environment of stable state on the macroscopic view in the reaction zone of reactor.By known technology make product be in decompression and (devolatilization) condition that heats up alternatively under be easy to reclaim product.This method is easy to remove silane or hydrocarbyl si lanes branching agent and inert diluent and the unreacted monomer of any remnants, as capable of circulation time reactor of needs.
Typically, the fluidized-bed of described vapor phase process is being higher than 50 ℃, preferred about 60 to about 110 ℃, more preferably from about 70 is operating to about 110 ℃ temperature.
The vapor phase process that is applicable to the inventive method has been described in many patents and patent application, and particularly U.S. Pat 4 588 790; 4 543 399; 5 352 749; 5 436 304; 5 405 922; 5,462 999; 5 461 123; 5 453 471; 5 032 562; 5 028 670; 5 473 028; 5 106 804; 5 556 238; 5 541 270; 5 608 019; 5 616 661; With EP 659773; 692 500; 780 404; 697 420; 628 343; 593 083; 676 421; 683 176; 699 212; 699 213; 721 798; 728 150; 728 151; 728 771; 728 772; 735 058; With WO-94/29032, WO-94/25497, WO-94/25495, WO-94/28032, WO-95/13305, WO-94/26793, WO-95/07942, WO-97/25355, WO-93/11171, WO-95/13305 and WO-95/13306, these documents all are incorporated herein for reference.
For the preferred polyolefin polymerization compositions of the present invention (available polymerization process of the present invention is produced with catalyst system of the present invention), it is long that described long-chain branch mixes the short-chain branch that main polymer chain produces than one or more alpha-olefin comonomer.Exist the experiment effect of long chain branching to show as the rheological enhancing in the polymkeric substance of the present invention, by flow-activation energy and I 21/ I 2Show than the height of estimating by other structural the subject of knowledge and the object of knowledge of composition.
Embodiment
Described the present invention, provide following examples to further specify and should not be construed as restriction.Can implement the present invention disclosed herein under the situation that does not have not concrete disclosed any component is conspicuous for those skilled in the art.Except as otherwise noted, all umbers and percentage are all based on weight.
Embodiment 1-9
All reactions and operation are all carried out under inert atmosphere in loft drier.Monomer and solvent pass through activated alumina and carried copper catalyzer (the Q5 reactant is available from Engelhardt company) purifying, and carry out other processing with the inert atmosphere technology of standard.Catalyst system therefor in the polymerization 6 and 7 (catalyst B) prepares in the following manner.
The 1H-pentamethylene is the preparation of [1] phenanthrene-2-base lithium also
To 1.42g (0.00657mol) 1H-pentamethylene being housed also in the 250ml round-bottomed flask of [1] luxuriant and rich with fragrance and 120ml benzene, the mixing hexane solution of dropping 4.2ml 1.60Mn-BuLi.This solution stirring is spent the night.Filter to isolate lithium salts, wash twice with 25ml benzene, vacuum-drying.Output is 1.426g (97.7%).1H NMR analyzes and shows that main isomer is 2 replacements.
The preparation of (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethylchlorosilane
To 4.16g (0.0322mol) dimethyldichlorosilane(DMCS) (Me is housed 2SiCl 2) and the 500ml round-bottomed flask of 250ml tetrahydrofuran (THF) (THF) in, drip the also THF solution of [1] phenanthrene-2-base lithium of 1.45g (0.0064mol) 1H-pentamethylene.With about 16 hours of solution stirring, under reduced pressure remove then and desolvate, obtain the oily solid, with the toluene extraction, by super-cell (Celite TM) filter, wash twice with toluene, drying under reduced pressure.Output is 1.98g (99.5%).
The preparation of (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethyl (uncle's fourth amino) silane
In the 500ml round-bottomed flask that 1.98g (0.0064mol) (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethylchlorosilane and 250ml hexane are housed, add 2.00ml (0.0160mol) TERTIARY BUTYL AMINE.Reaction mixture was stirred several days, use super-cell (Celite then TM) filter, wash twice with hexane.Under reduced pressure remove residual solvent and isolate product.Output is 1.98g (88.9%).
The preparation of (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethyl (uncle's fourth amino) silane two lithiums
In the 250ml round-bottomed flask that 1.03g (0.0030mol) (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethyl (uncle's fourth amino) silane and 120ml benzene are housed, drip the mixing hexane solution of 3.90ml 1.6Mn-BuLi.With reaction mixture stir about 16 hours.Filter to isolate product, wash twice, drying under reduced pressure with benzene.Output is 1.08g (100%).
Dichloro (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethyl (uncle's fourth amino) silane closes the system of titanium Be equipped with
To 1.17g (0.0030mol) TiCl is housed 3In the 250ml round-bottomed flask of 3THF and about 120ml THF, with the fast THF solution that drips speed adding about 50ml (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethyl (uncle's fourth amino) silane two lithiums (1.08g).Mixture was stirred 1.5 hours down at about 20 ℃, add 0.55g (0.002mol) solid PbCl simultaneously 2Behind the restir 1.5 hours, remove THF under vacuum, resistates extracts with toluene, filters, and decompression is dry down, obtains orange solids.Output is 1.31g (93.5%).
1,4-diphenyl diethylene (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethyl (uncle's fourth amino) Silane closes the preparation of titanium
Close titanium (3.48g to 70 ℃ dichloros (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethyl (uncle's fourth amino) silane, 0.0075mol) (producing by amplifying embodiment 1) and 1.55g (0.0075mol) 1, in the toluene of 4-diphenyl diethylene (about 80ml) slurries, add 9.9ml1.6Mn-BuLi (0.0150mol) solution.Solution is blackening immediately.Intensification refluxes mixture, and mixture was kept 2 hours in this temperature.Mixture is cooled to-20 ℃ approximately, under reduced pressure removes volatile matter.Resistates was suspended in about 20 ℃ 60ml mixing hexane about 16 hours.With mixture be cooled to approximately-25 ℃ about 1 hour.By vacuum filtration with solid collection on frit, drying under reduced pressure.The exsiccant solid is placed in the glass fibre sleeve, utilizes Soxhlet's extractor to use hexane extraction continuously.After 6 hours, in still kettle, observe crystalline solid.Mixture is cooled to-20 ℃ approximately, and with the cold mixt filtering separation, drying under reduced pressure obtains 1.62g black crystalline solid.Filtrate is discarded.Solid in the stirring extractor continues the mixing hexane extraction with additional content, and the 0.46gm that gets back wants product, is black crystalline solid.
Metal complexes B can be described by following structural representation:
Isopar-E is being housed TMCarry out polymerization in 2 liters of Pa Er reactors of the comonomer of combination chain alkane solvent (available from Exxon chemical company) and required amount.Add silane (SiH by the 75ml feed pot by the differential pressure expansion 4).Reactor is heated to the initial reaction temperature of requirement, makes it stable.The catalyzer of the amount of requirement and promotor (three (pentafluorophenyl group) borine) are obtained the catalyzer and the promotor of 1: 1 mol ratio with toluene solution form premix in dried case, add polymerization reactor by the stainless steel transfer lime with nitrogen and toluene " chaser ".Make the reaction times shown in the polymerizing condition maintenance with ethene as required, periodically add catalyzer to keep polymerization activity.Remove reaction heat continuously by inner spiral coil cooling tube.After time, from reactor, take out gained solution shown in the polymerization, use the Virahol quenching, add hindered phenol antioxidant (Irganox TM1010, from CibaGeigy company) make it stable.In vacuum drying oven, remove by about 16 hours of heated polymerizable thing solution under 140 ℃ and desolvate.The results are shown in the table 1.
Table 1
Embodiment Catalyzer (μ mol) Temperature (℃) Time (min.) Silane (Δ MPa) C 2H 4 (MPa) C 3H 7 (g) Vinylbenzene (g) Isopar (g) Output (g) Mw ×10 6 Mn ×10 6 Mz ×10 6
1 A(1.3) 140 22.5 0.3 3.4 0 0 860 15.5 575 249 988
2 A(1.5) “ 15.4 0.7 “ “ “ “ 7.3 466 182 761
3 A(6.3) “ 30.5 1.4 “ “ “ “ 11.2 434 186 732
4 A(8.0) 90 30.5 0.7 1.4 “ 456 360 61.7 124 48 214
5 A(8.0) “ 30.6 1.4 “ “ “ “ 47.3 92 47 145
6 B(7.0) “ 30.6 0.7 “ “ “ “ 59.5 107 50 260
7 B(20.0) “ 51.7 1.4 “ “ “ “ 69.2 76 34 234
8 C(6.0) 70 15.8 0.7 0 150 0 650 76.9 12 6 19
9 C(6.0) “ 14.2 1.4 “ “ “ “ 82.4 10 6 15
A=(1,3-pentadiene) (uncle's fourth amino) (tetramethyl-ring pentadienyl) dimethylsilane closes titanium
B=1,4-diphenyl diethylene (the 1H-pentamethylene is [1] phenanthrene-2-yl also) dimethyl (uncle's fourth amino) silicomethane closes titanium
C=(anti-, anti--1,4-phenylbenzene-1,3-butadiene) (ethylene two (1-indenyl)) closes zirconium
Embodiment 10-13
Continuous gas-phase polymerization
Carry out continuous gas-phase polymerization in 6 liters Gas-phase reactor, this reactor has by the continuous 2 inches diameter of the zone of transition of conical wall, grows 12 inches fluidization regions and 8 inches of diameters, grows 8 inches reduction of speed district.Typical operation conditions comprises: 40 to 100 ℃ of temperature, and stagnation pressure 100 is to 350psia, and the reaction times was up to 8 hours.Monomer, comonomer and other gas enter reactor bottom, pass through gas distribution grid.Gas flow rate is 2 to 8 times of smallest particles fluidizing velocity [FluidizationEngineering, the 2nd edition, D.Kuni and O.Levenspiel, 1991, Butterworth-Heinemann].Most suspended solidss break away from the reduction of speed district.Gas leaves top, reduction of speed district, removes any particulate by dust filter.This gas is by the gas boosting pump then.Polymkeric substance gathers in reactor in the reaction process.Make the stagnation pressure of system keep constant by the flow of monomer of regulating inflow reactor between the reaction period.Open a series of valves that are arranged in the fluidization regions bottom and make polymer discharge, make polymkeric substance move to returnable from reactor to the returnable that remains below reactor pressure.The pressure of the monomer of being reported, comonomer and other gas refers to dividing potential drop.
In the glove box of inert atmosphere, prepare catalyzer, in the catalyst injection device of packing into.From glove box, take out syringe, insertion reaction device top.Adding an amount of monomer, comonomer and other gas in reactor makes stagnation pressure meet the requirements of reaction pressure.Inject catalyzer then, made accumulation of polymer 30 to 90 minutes.Make system's stagnation pressure keep constant by the flow of monomer of regulating inflow reactor between the reaction period.After 30 to 90 minutes, with the reactor emptying, the collected polymer powder.
Embodiment 10
With 15.9g Crosfield type ES70Y silica (surface-area=315m 2/ g, Malvern granularity [D50]=106.8 μ m) in inert nitrogen stream, heated 4 hours under 500 ℃.Silica is cooled to room temperature in inert nitrogen stream.Seal the two ends of silica roasting pipe then, put into the glove box of inert atmosphere.From the roasting pipe, take out silica, be suspended in the 80ml hexane with the ratio of 5ml hexane/g silica.In these silica slurries, add triethyl aluminum (TEA) solution of 2.93g 93% weight, be equivalent to 1.5mmol TEA/g silica.These slurries were placed 2 hours, manually leniently stirred in per 15 to 20 minutes.After 2 hours, filter this silica, wash twice (100ml altogether) with hexane and remove issuable any soluble aluminum compound in described TEA treatment step.Then silica drying under the room temperature vacuum is obtained free-pouring powder.
Make a five equilibrium (160 μ l) 0.005M (0.8 μ mol) (η 5-C 5Me 4SiMe 2NCMe 3)-Ti (η 4-C 5H 8) toluene solution with mix with the pre-wetting above-mentioned pretreated Crosfield type ES70Y silica of 0.03g of～200 μ l dry toluenes.Then with a five equilibrium (180 μ l) 0.005M (0.9 μ mol) B (C 6F 5) 3Toluene solution add in the described silica slurries.Removing desolvates obtains free-pouring powder.The catalyzer of as above preparation is added in the gas-phase fluidized-bed reactor, and described reactor is under the nitrogen pressure of the tetrahydrochysene silane pressure of 1-butylene pressure, 2psi (14kPa) of ethylene pressure, the 5psi (34kPa) of 240psi (1.7MPa) and 50psi (340kPa).Temperature is 70 ℃ in the whole polymerization process.Analyze by NMR, the polymkeric substance that is reclaimed contains at least 4.0 long-chain branchs/10000 carbon.
Embodiment 11
(s-instead-instead to make a five equilibrium (200 μ l) 0.005M, instead-1,4-phenylbenzene-1,3-butadiene) [ethylene two (1-indenyl)] closes the toluene solution of zirconium and mixes with Crosfield ES70Y silica pretreated described in the wetting in advance 0.03g embodiment 10 of 200 μ l toluene.Then a five equilibrium (220 μ l) 0.005M three (pentafluorophenyl group) borine solution is added in these slurries.After this mixture shaken 10 minutes, under vacuum, remove to desolvate and obtain free-pouring powder.
The catalyzer of as above preparation is added in the gas-phase fluidized-bed reactor, and described reactor is under the nitrogen pressure of the silane pressure of 1-butylene pressure, 2psi (14kPa) of ethylene pressure, the 5psi (34kPa) of 240psi (1.7MPa) and 50psi (340kPa).Temperature remains on 70 ℃ in the whole polymerization process.Reclaim the polyethylene polymer that obtains containing long chain branching after 30 minutes.
Embodiment 12
(s-instead-instead to make a five equilibrium (400 μ l) 0.00500M, instead-1,4-phenylbenzene-1,3-butadiene) [ethylene two (1-indenyl)] closes the toluene solution of zirconium and mixes with Crosfield ES70Y silica pretreated described in the wetting in advance 0.03g embodiment 10 of 200 μ l toluene.Then a five equilibrium (420 μ l) 0.005M three (pentafluorophenyl group) borine solution is added in these slurries.After this mixture shaken 10 minutes, under vacuum, remove to desolvate and obtain free-pouring powder.
The catalyzer of as above preparation is added in the gas-phase fluidized-bed reactor, and described reactor is under the nitrogen pressure of the silane pressure of propylene pressure, 2psi (14kPa) of 100psi (700kPa) and 20psi (140kPa).Temperature remains on 70 ℃ in the whole polymerization process.Be recovered to the crystalline polypropylene polymkeric substance that contains long chain branching after 60 minutes.
Embodiment 13
CroSfield type ES70Y silica (granularity=40 μ m) was heated 4 hours under 250 ℃ in inert nitrogen stream.Silica is cooled to room temperature in inert nitrogen stream.Seal the two ends of silica roasting pipe then, put into the glove box of inert atmosphere.From the roasting pipe, take out silica, the 5g silica is suspended in hexane (50ml) solution of 5ml triethyl aluminum (TEA).These slurries were placed 15 minutes, manually leniently stirred occasionally.Then, filter this silica, give a baby a bath on the third day after its birth with hexane and remove issuable any soluble aluminum compound in described TEA treatment step all over (150ml altogether).Then silica drying under the room temperature vacuum is obtained free-pouring powder.
In the TEA of 0.400ml 0.150M solution, add 0.400ml toluene.The toluene solution that in this solution, adds 0.400ml 0.150M three (pentafluorophenyl groups) (4-hydroxyphenyl) boric acid methyl two (octadecyl) ammonium.Make this solution left standstill 10 minutes, add the above-mentioned pretreated silica of 1.000g then.Mixture is thoroughly mixed, make it to leave standstill 5 minutes, add the 10ml hexane this moment.In this mixture, add 33.2mg (anti-, anti--1,4-phenylbenzene-1,3-butadiene) [two (2-methyl-4-phenyl-1-indenyl) dimethylsilane] and close hexane (10ml) solution of zirconium.Shake the gained mixture then.After 20 hours, decantation goes out supernatant liquid carefully from settled solid.Then the 12ml hexane is added in this solid.With slurries in two, only half is used for the remainder of this embodiment.The hexane that the 12.5ml propylene is saturated adds in these half slurries, stirs 5 minutes.Decantation goes out supernatant liquid from settled solid.Volatile matter is evaporated from solid.
The catalyzer of as above preparation is added in the gas-phase fluidized-bed reactor, and described reactor is under the nitrogen pressure of the silane pressure of propylene pressure, 2psi (14kPa) of 100psi (700kPa) and 20psi (300kPa).Temperature remains on 70 ℃ in the whole polymerization process.Recovery obtains containing the crystalline polypropylene polymkeric substance of long chain branching.
Embodiment 14
The preparation of catalyst component
1.Kemamine TM The preparation of the hydrochloride of T9701
Make Kemamine available from Witco company TMT9701 (NMe (C 18-22H 37-45) 2(13.4g, 25mmol) (Kemamine is the trade mark of Witco company) is dissolved in the diethyl ether (300ml).Make the hydrogen chloride gas bubbling pass through this solution 5 minutes, show that up to the pH test paper its pH is for acid.Mixture was stirred 15 minutes, filter and collect white precipitate, give a baby a bath on the third day after its birth all over (every), vacuum-drying all over using the 50ml diethyl ether with diethyl ether.NHClMe (C 18-22H 37-45) 2Output be 12.6g.
2.[(p-HOC 6H 4) B (C 6F 5) 3] [NHMe (C 18-22H 37-45) 2] Preparation
Make NHClMe (C 18-22H 37-45) 2(4.58g 8mmol) is dissolved in the methylene dichloride (50ml).Add three (pentafluorophenyl groups) (4-hydroxyphenyl) boric acid triethyl ammonium [(p-HOC 6H 4) B (C 6F 5) 3] [NHEt 3] (5.66g, 8mmol prepare basically as described in the USSN08/610 647 (corresponding to WO96/28480) of application on March 4th, 1996), add 40ml distilled water then.Mixture was stirred 4 hours fast, remove water layer with syringe then.Dichloromethane layer is given a baby a bath on the third day after its birth all over (every all over 40ml) with distilled water.Make dichloromethane layer through dried over sodium sulfate then, filter, vacuum-drying produces oil.This oil is extracted in the toluene (200ml),, makes filtrate vacuum-drying obtain the 8.84g water white oil the gained solvent filter.
3. the preparation of support of the catalyst
The silica SP12 (Grace Davison XPO2402) that 40g has been heated 3 hours under 250 ℃ of vacuum is suspended in the toluene (400ml), and the 40ml triethyl aluminum (TEA) that is used in then in the 250ml toluene is handled.Mixture was stirred 1 hour, filter, the silica of handling is with toluene (100ml is under about 100 ℃) washing, and is dry under high vacuum.
B. the preparation of loaded catalyst
Make 0.4ml 0.1M[(p-HOC 6H 4) B (C 6F 5) 3] [NHMe (C 18-22H 37-45) 2] toluene solution mixed about 10 minutes with the toluene solution of 0.4ml 0.1M triethyl aluminum, add 0.4ml toluene.Gained solution is divided into three parts, adds the described silica of handling with TEA of 1g subsequently.Shake the gained mixture, add the 20ml hexane, shake again.After dry 30 minutes, under agitation will be dissolved in the 33.2mg 1 in the 1.2ml toluene in a vacuum, 4-phenylbenzene-1,3-butadiene racemize-dimethylsilane two (2-methyl-4-phenyl-indenes-1-yl) closes zirconium (by US5 278 264 preparations) and adds in this silica.Then with gained catalyzer hexane wash, drying.Find that this catalyzer contains 35 μ molZr/g carriers.
C. polymerization
2 liters of Pa Er reactors are heated to 70 ℃, and the 270g propylene of packing into is used the 0.14L pressurized with hydrogen.Will based on the monomer total amount be 0.13wt%, be dissolved in the 0.5ml toluene and use N 2Be forced in 7-octenyl silane (containing the 14.6%6-octenyl silane of having an appointment) this container of packing into than the high 100psig of reactor pressure.Then at N than the high 100psig of reactor pressure 2Pressure adds down 12 μ mol and is suspended in the described Zr of containing catalyzer in the hexane with initiated polymerization.Polymerization continues 30 minutes, produces the silane-modified polypropylene of 45.3g octenyl.The MWT of this polymkeric substance is 459 000, and MWD is 3.2.Compare with the polypropylene for preparing under the contrast condition, this multipolymer contains the LCB of increase, and showing as soltion viscosity increases with absolute molecular weight, and strain hardening increases with the increase of rate of extension in the extensional flow.Analyze based on this, this polymkeric substance that contains octenyl silane has 0.2-0.5 four sense branching position/bar chains.
Embodiment 15
With catalyzer and the polymerization process of embodiment 14, make octene silane and the copolymerization of propylene of 0.25wt%, obtain the silane-modified polypropylene of 28.7g 7-octenyl.The MWT of this polymkeric substance is 440000, and molecular weight distribution (MWD) is 3.4.Compare with the polypropylene for preparing under the contrast condition, this multipolymer contains the LCB of increase, and showing as soltion viscosity increases with absolute molecular weight, and strain hardening increases with the increase of rate of extension in the extensional flow.Analyze based on this, this polymkeric substance that contains octenyl silane has 0.2-0.5 four sense branching position/bar chains.
Embodiment 16
With catalyzer and the polymerization process of embodiment 14, make octene silane and the copolymerization of propylene of 0.5wt%, obtain the silane-modified polypropylene of 4.8g 7-octenyl.The MWT of this polymkeric substance is 335000, and MWD is 4.2.Compare with the polypropylene for preparing under the contrast condition, this multipolymer contains the LCB of increase, and showing as soltion viscosity increases with absolute molecular weight, and strain hardening increases with the increase of rate of extension in the extensional flow.Analyze based on this, this polymkeric substance that contains octenyl silane has 0.2-0.5 four sense branching position/bar chains.
Embodiment 17 (contrast)
With catalyzer and the polymerization process of embodiment 14, polypropylene under the situation that does not have silane obtains the 45.3g polypropylene.The MWT of this polymkeric substance is 351000, and MWD is 2.8.

Claims (5)

1. but the preparation method of the homopolymer of addition polymerization olefinic monomer or these monomeric mixtures and multipolymer, described method comprises contacts described monomer or monomer mixture with following catalyst composition under the polymerizing condition of the high monomer transformation efficiency of the pressure of 0 to 160 ℃ temperature and 6.9KPa to 3.4MPa, described catalyst composition comprises:
A) corresponding to the metal complex of following formula:
Figure C998026310002C1
Or
Figure C998026310002C2
Wherein:
M is titanium, zirconium or hafnium;
R 3When occurring at every turn independently for being selected from alkyl, silylation, germane base, halogen, halo alkyl,-oxyl, silicon alkyl oxyalkyl, N, N-two (silicon alkyl alkyl) amino, N-alkyl-N-silylation amino, N, the alkyl that N-two (alkyl) is amino, alkylene is amino, two (alkyl) phosphino-, sulfenyl or-oxyl replace, described R 320 non-hydrogen atoms are arranged, perhaps adjacent R at most 3Thereby base form together divalent derivative form the condensed ring system and
X " be the anion ligand base of maximum 40 non-hydrogen atoms, perhaps two X when occurring independently at every turn " form the dianion part base of maximum 40 non-hydrogen atoms together,
The derivative that replaces for the neutral conjugation diene of maximum 40 non-hydrogen atoms or its silylation, germane base or halo alkyl independently when X occurs at every turn;
E is silicon or carbon,
When R ' occurs at every turn independently for hydrogen or be selected from the group of silylation, alkyl,-oxyl and combination thereof, described R ' have maximum 30 carbon or Siliciumatom and
X is 1 to 8; With
B) corresponding to the hydrocarbyl si lanes of following formula:
A nJ jSiH 4-(n+j)
Wherein:
J is C 1-40Alkyl,
A is C 2-20Alkenyl,
N be 1 or 2 and
J is 0 or 1;
And lasting polymerization has 50 up to polymkeric substance, 000-600, and 000 Mw and comprise 0.1 to 100 long-chain branch/10,000 carbon, partial polymer comprises silane branching center at least.
2. the process of claim 1 wherein that hydrocarbyl si lanes is a 7-octene silane.
3. the process of claim 1 wherein that transition metal complex is (instead, anti--1,4-phenylbenzene-1,3-butadiene) (ethylene two (1-indenyl)) closes zirconium or (anti-, instead-1,4-phenylbenzene-1,3-butadiene) [two (2-methyl-4-phenyl-1-indenyl) dimethylsilane] closes zirconium.
4. the process of claim 1 wherein that the number of described long-chain branch is 0.3 to 10/10,000 carbon.
5. each method of aforementioned claim, wherein said monomer is a propylene.
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